Electronic Stability of Phosphine-Protected Au<sub>20</sub> Nanocluster: Superatomic Bonding

Yuan, Yuan; Cheng, Longjiu; Yang, Jinlong

doi:10.1021/jp402816b

Cited by 47 publications

(63 citation statements)

References 89 publications

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“…The n * value of Au 20 6+ is 14, equivalent to Au 25 11+ . This suggests that the Au 20 6+ (14e) core is composed of pseudo‐halogen Au 11 4+ (7e) superatoms with an electronic configuration of (1S) 2 (1P) 5 through a covalent‐like bonding . The strong interaction between superatoms is supported by the optical absorption spectrum as well (Figure e).…”

Section: Ligand‐protected Gold Superatomic Moleculesmentioning

confidence: 73%

Chemically Modified Gold Superatoms and Superatomic Molecules

Nishigaki

Koyasu

Tsukuda

2014

The Chemical Record

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Clusters of gold atoms can be viewed as superatoms, in which valence electrons confined in the particles occupy atomic-like, discrete electronic levels. Chemical modification of the gold superatoms and their aggregated molecules (superatomic molecules) with organic ligands is a promising approach for their application as the building units of new functional materials. This account surveys the present status of the rapidly growing field of gold superatoms and superatomic molecules protected by thiolates and phosphines. The major aim of this article is to provide a simple picture for the structure, stability and bonding scheme of chemically modified superatoms and superatomic molecules for the development of a new class of hierarchical materials.

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Section: Ligand‐protected Gold Superatomic Moleculesmentioning

confidence: 73%

Chemically Modified Gold Superatoms and Superatomic Molecules

Nishigaki

Koyasu

Tsukuda

2014

The Chemical Record

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“…Interestingly, the electronic structures of some prolate superatoms can be understood by viewing them as quasi‐molecules composed of superatoms (“superatomic molecules”). [ 119,150–154 ] According to the super valence bond theory developed by Yang and Chen, [ 153,154 ] the prolate Au 20 (14e) and Au 23 (14e) superatoms can be viewed as dimers of open‐shell Au 11 (7e) and Au 13 (7e) superatoms linked by sharing an edge (Au + ) 2 or facet (Au + ) 3 , respectively (Table 6) [ 144–147,153,154 ]

\begin{matrix} 2 A {boldnormalu}_{11} (7 e) - {({Au}^{+})}_{2} = A {boldnormalu}_{20} (14 e) \end{matrix}

\begin{matrix} 2 A {boldnormalu}_{13} (7 e) - {({Au}^{+})}_{3} = A {boldnormalu}_{23} (14 e) \end{matrix}

…”

Section: Effect Of Shape: Nonspherical Superatomsmentioning

confidence: 99%

Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

Omoda

Takano

Tsukuda

2020

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Atomically precise gold/silver clusters protected by organic ligands L, [(Au/Ag)xLy]z, have gained increasing interest as building units of functional materials because of their novel photophysical and physicochemical properties. The properties of [(Au/Ag)xLy]z are intimately associated with the quantized electronic structures of the metallic cores, which can be viewed as superatoms from the analogy of naked Au/Ag clusters. Thus, establishment of the correlation between the geometric and electronic structures of the superatomic cores is crucial for rational design and improvement of the properties of [(Au/Ag)xLy]z. This review article aims to provide a qualitative understanding on how the electronic structures of [(Au/Ag)xLy]z are affected by geometric structures of the superatomic cores with a focus on three factors: size, shape, and composition, on the basis of single‐crystal X‐ray diffraction data. The knowledge accumulated here will constitute a basis for the development of ligand‐protected Au/Ag clusters as new artificial elements on a nanometer scale.

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“…18,[24][25][26][27][28][29][30] Its structure is that of a bulk face-centered cubic (fcc) gold fragment, in a finite nanosized cluster motif. 18,26 Efforts to bring [Au 20 ] species into solution has been carried out since the last ten years, 26,[31][32][33][34][35] which resulted in structures and electronic structures completely different from that of the 37,38 was a first example of the capability of Group 11 cores to be embedded in an outer shell made of organometallic units, which can increase the versatility of the protecting layer.…”

Section: +1mentioning

confidence: 99%

[M₁₆Ni₂₄(CO)₄₀]^4–: Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au₂₀ Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations

et al. 2018

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Characterization of the tetrahedral Au 20 structure in the gas-phase remains as a major landmark in gold cluster chemistry, where further efforts to stabilize this bare 20-electron superatom in solution, to extend and understand its chemistry have failed so far. Here, we account for the structural, electronic and bonding properties of [M 16 Ni 24 (CO) 40 ] 4-(M = Cu, Ag, Au) observed in solution for gold and silver. Our results show a direct electronic relationship with Au 20 , owing that such species share a common tetrahedral [M 16 ] 4central core with a 1S 2 1P 6 1D 10 2S 2 jellium configuration. In the case of Au 20 , the [Au 16 ] 4core is capped by four Au + ions, whereas in [M 16 Ni 24 (CO) 40 ] 4it is capped by four Ni 6 (CO) 10 units. In both cases, the capping entities are full part of the superatom entity where appears that the free (uncapped) [M 16 ] 4species requires to be capped for further stabilization. It follows that the Ni 6 (CO) 10 units in [M 16 Ni 24 (CO) 40 ] 4should not be considered as external ligands as their bonding with the [M 16 ] 4core is mainly associated with a delocalization of the 20 jellium electrons onto the Ni atoms. Thus, the [M 16 Ni 24 (CO) 40 ] 4species can be seen as the solution version of tetrahedral M 20 clusters, encouraging experimental efforts to further develop the chemistry of such complexes as M(111) finite surface section structures, with M=Ag and Au and, and particularly promising with M=Cu. Furthermore, optical properties were simulated to assist future experimental characterization. Relevant computed data for [M 16 ] 4and [M 20 ] clusters (M=Cu, Ag, Au) of jellium configuration 1S 2 1P 6 1D 10 2S 2 , and Kohn-Sham jellium orbitals of [Au ] 4and [Au 20 ]. Major electronic absorption for [M 16 Ni 24 (CO) 40 ] 4-(M = Cu, Ag, Au) computed at the PBE and BP86 levels. This material is available free of charge via the Internet at http://pubs.acs.org.

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Electronic Stability of Phosphine-Protected Au₂₀ Nanocluster: Superatomic Bonding

Cited by 47 publications

References 89 publications

Chemically Modified Gold Superatoms and Superatomic Molecules

Chemically Modified Gold Superatoms and Superatomic Molecules

Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

[M₁₆Ni₂₄(CO)₄₀]^4–: Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au₂₀ Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations

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Electronic Stability of Phosphine-Protected Au20 Nanocluster: Superatomic Bonding

Cited by 47 publications

References 89 publications

Chemically Modified Gold Superatoms and Superatomic Molecules

Chemically Modified Gold Superatoms and Superatomic Molecules

Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

[M16Ni24(CO)40]4–: Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au20 Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations

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Resources

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Electronic Stability of Phosphine-Protected Au₂₀ Nanocluster: Superatomic Bonding

[M₁₆Ni₂₄(CO)₄₀]^4–: Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au₂₀ Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations